CA1103830A - Fire retardant acrylic terpolymer composition and films thereof - Google Patents
Fire retardant acrylic terpolymer composition and films thereofInfo
- Publication number
- CA1103830A CA1103830A CA290,361A CA290361A CA1103830A CA 1103830 A CA1103830 A CA 1103830A CA 290361 A CA290361 A CA 290361A CA 1103830 A CA1103830 A CA 1103830A
- Authority
- CA
- Canada
- Prior art keywords
- fire retardant
- phosphate
- triorgano
- film
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
Abstract
ABSTRACT OF THE DISCLOSURE
Flame retardant acrylic terpolymer compositions comprise the reaction product of (1) an alkyl acrylate or alkyl methacrylate where the alkyl radical contains 1 to 16 carbon atoms, (2) vinyl nitrile, and (c) a halogenated monomer selected from the class consisting of vinylidene chloride, halogenated phenyl acrylate, halogenated phenyl , compounded with a flame retardant plasticizer of triorgano phosphate, either alone or combined with decabromodiphenyl oxide or tris (B - chloroethyl) phosphate or the metal oxides of antimony and zinc, said compositions being useful as a film.
Flame retardant acrylic terpolymer compositions comprise the reaction product of (1) an alkyl acrylate or alkyl methacrylate where the alkyl radical contains 1 to 16 carbon atoms, (2) vinyl nitrile, and (c) a halogenated monomer selected from the class consisting of vinylidene chloride, halogenated phenyl acrylate, halogenated phenyl , compounded with a flame retardant plasticizer of triorgano phosphate, either alone or combined with decabromodiphenyl oxide or tris (B - chloroethyl) phosphate or the metal oxides of antimony and zinc, said compositions being useful as a film.
Description
This lnvention relates to novel fire retardant acrylic terpolymer composi-tions and films made from said composi-tion.
More par-ticularly, this inven-tion rela-tes to plas-ticized acrylic -terpolymer composi-tions suitable for making films -that pass the NFPA701 vertical flame test with rela-tively lo~ fire re-tardan-t additive loading.
The acryla-te polymers and copolymer composi-tions have required compou~ding with very high loadings of fire retar-dant additive to pass the vertical flame test of Method NFPA
701 but the high additive loadings have lowered the physical properties (tensile and modulus) of the compounded acr~late polymer or copolymer compositions. Therefore, their use in films or related products have not been widely accepted.
Unexpectedly, I ha~e discovered that some of the acry-lic -terpolymers can be compounded with relatively small amounts (less than 35 percent by weight) of fire retardant additives and pass the MFPA701 vertical flame test and the - resul-ting compounded acrylate terpolymers have good tensile strength and elongation and further exhibit good retention of physical properties a~ter 300 hours ~ccelerometer aging, Thus, these compounded acryla-te terpolymers yield ~ilms well -suited for inflatable structures, packaging films~ top coat-ings for floor tile and wall coverings and pond liners.
The flame retardant acrylic terpolymer compositions comprise an acrylic terpolymer of the mono~ers o~ Class A, B
and C, usually about 20 to 60 parts of A, 10 to 40 parts of B and 20 to 70 parts of C and a fire retardant additive, usually as a plasticizer~ -Representative monomers of Class A are the alkyl acry---1~
~38;~
late and alkyl methacryla-tes where the alkyl radical contains from one to abou-t 16 carbon atoms, especially preferred al~yl radicals are me-thyl, ethyl, bu-tyl and 2-ethylhexyl (2-E~).
Representatlve monomers o~ Class B are acryloni-trile (AN), methacrylonitrile (MAN) and ethacrylonitrile~
Representative monomers of Class C are vinylidene chlo-ride (also abbreviated as VDC), pentachlorophenyl methacrylate (also abbrevia-ted PCMA), 2~4,6-tribromophenyl methacrylate (also abbrevia-ted TBMA), as well as the halogenated phenyl lQ acryla-tes and phenyl methacrylates containing about 20 to 70 and pre~erably 50 to 60 percent by weight of halogen such as chloride or bromide.
Representa-tive fire retardant additives are the primary addi-tives, the -triorgano phosphates, sometimes called organo-phosphate esters, -those called the complementary additives, and the metal oxides of zinc and antimony, and the halogena-ted hydrocarbons. The triorgano phosphates are grouped generally as aryl, alkylaryl, alkyl and cycloalkyl, where the aryl and cycloalkyl radical contains 6 to 10 carbon atoms and the alkyl radical contains 1 to 20 carbon ato~s. The tri-organo phosphates can be triaryl, trialkyl, tricycloalkyl or mixtures of these radicals. Represen-tative radicals of these triorgano phosphates are -triphenyl, tricresyl~ xenyl, tritert-bu-tylphenyl, tertamylphenyl and their homologuesJ ~ lritertbu-tyl, tritertamyl, 2-ethylhexyl diphenyl, isodecyl diphenyl~
tributyl, trioctyl, tributoxyethyl, tris(2,3-dichloropropyl) and tris(2,3-dibromopropyl). Mixed commercial grade triorgano - phosphates are available as mixed triaryl phosphates, ab~re-viated as TAP, and isodecyl diphenyl phospha-te, abbreviated 3~
as IDDPP. The complementary additives are representecl by tris(betachloroethyl) phosphate, abbreviated as TBCEP, decabromodiphenyl oxide, hereinafter DBDP0.
Distearyl pentaerythritol diphosphite, hereinafter called W-618 and a liquid tin maleate as a thermcl~ stabi.l:izer, hereinafter called F-837 are additives someti.mes useful to stab:i.l:ize tlle polynler to relat:i.vely h:igh temperatures.
ln pa.rt:i.culclr, i.ll accordance w:ith the present :i.nvention, there is prov:ided a flame re~arclant polymer fi.lm comprising a terpolymer and about 10 to 40 parts of a fire retardant plasticizer per 100 parts of polymer, said terpolymer being a reaction product of (1) 20 to 60 weight percent 2-ethylhexyl acrylate, (2) 10 to 40 weight percent acrylonitrile, and (3) 20 to 70 weight percent halogenated monomer selected from the class consisti.ng of vinylidene chloride, halogenated phenyl acrylate, halogenated phenyl methacrylate containing 20 to 70 percent by weight of halogen and the fire retardant plasticizer being selected from the class consisting of a triorgano phosphate, alone or in combination with decabromodiphenyl oxide and metal oxides of antimony and zinc.
Preferably, the terpolymer is an addition polymer of 2-ethylhexyl acrylate, acrylonitrile and a third monomer selected from the class consisting of vinylidene chloride, pentachlorophenyl methacrylate and 2,4,6-tribromophenyl methacrylate.
Furthermore and preferably the fire retardant additive contains a triorgano phosphate in combination with at least one complementary additive selected from the class of decabromodiphenyl oxide, antimony o~ide and zinc oxide.
It has been found that the above compositions can be formed into films or other shapes having improved resistance to aging by incorporation of 0.5 to 4 parts, and preferably 1 to 2 parts of a light stabilizer such as
More par-ticularly, this inven-tion rela-tes to plas-ticized acrylic -terpolymer composi-tions suitable for making films -that pass the NFPA701 vertical flame test with rela-tively lo~ fire re-tardan-t additive loading.
The acryla-te polymers and copolymer composi-tions have required compou~ding with very high loadings of fire retar-dant additive to pass the vertical flame test of Method NFPA
701 but the high additive loadings have lowered the physical properties (tensile and modulus) of the compounded acr~late polymer or copolymer compositions. Therefore, their use in films or related products have not been widely accepted.
Unexpectedly, I ha~e discovered that some of the acry-lic -terpolymers can be compounded with relatively small amounts (less than 35 percent by weight) of fire retardant additives and pass the MFPA701 vertical flame test and the - resul-ting compounded acrylate terpolymers have good tensile strength and elongation and further exhibit good retention of physical properties a~ter 300 hours ~ccelerometer aging, Thus, these compounded acryla-te terpolymers yield ~ilms well -suited for inflatable structures, packaging films~ top coat-ings for floor tile and wall coverings and pond liners.
The flame retardant acrylic terpolymer compositions comprise an acrylic terpolymer of the mono~ers o~ Class A, B
and C, usually about 20 to 60 parts of A, 10 to 40 parts of B and 20 to 70 parts of C and a fire retardant additive, usually as a plasticizer~ -Representative monomers of Class A are the alkyl acry---1~
~38;~
late and alkyl methacryla-tes where the alkyl radical contains from one to abou-t 16 carbon atoms, especially preferred al~yl radicals are me-thyl, ethyl, bu-tyl and 2-ethylhexyl (2-E~).
Representatlve monomers o~ Class B are acryloni-trile (AN), methacrylonitrile (MAN) and ethacrylonitrile~
Representative monomers of Class C are vinylidene chlo-ride (also abbreviated as VDC), pentachlorophenyl methacrylate (also abbrevia-ted PCMA), 2~4,6-tribromophenyl methacrylate (also abbrevia-ted TBMA), as well as the halogenated phenyl lQ acryla-tes and phenyl methacrylates containing about 20 to 70 and pre~erably 50 to 60 percent by weight of halogen such as chloride or bromide.
Representa-tive fire retardant additives are the primary addi-tives, the -triorgano phosphates, sometimes called organo-phosphate esters, -those called the complementary additives, and the metal oxides of zinc and antimony, and the halogena-ted hydrocarbons. The triorgano phosphates are grouped generally as aryl, alkylaryl, alkyl and cycloalkyl, where the aryl and cycloalkyl radical contains 6 to 10 carbon atoms and the alkyl radical contains 1 to 20 carbon ato~s. The tri-organo phosphates can be triaryl, trialkyl, tricycloalkyl or mixtures of these radicals. Represen-tative radicals of these triorgano phosphates are -triphenyl, tricresyl~ xenyl, tritert-bu-tylphenyl, tertamylphenyl and their homologuesJ ~ lritertbu-tyl, tritertamyl, 2-ethylhexyl diphenyl, isodecyl diphenyl~
tributyl, trioctyl, tributoxyethyl, tris(2,3-dichloropropyl) and tris(2,3-dibromopropyl). Mixed commercial grade triorgano - phosphates are available as mixed triaryl phosphates, ab~re-viated as TAP, and isodecyl diphenyl phospha-te, abbreviated 3~
as IDDPP. The complementary additives are representecl by tris(betachloroethyl) phosphate, abbreviated as TBCEP, decabromodiphenyl oxide, hereinafter DBDP0.
Distearyl pentaerythritol diphosphite, hereinafter called W-618 and a liquid tin maleate as a thermcl~ stabi.l:izer, hereinafter called F-837 are additives someti.mes useful to stab:i.l:ize tlle polynler to relat:i.vely h:igh temperatures.
ln pa.rt:i.culclr, i.ll accordance w:ith the present :i.nvention, there is prov:ided a flame re~arclant polymer fi.lm comprising a terpolymer and about 10 to 40 parts of a fire retardant plasticizer per 100 parts of polymer, said terpolymer being a reaction product of (1) 20 to 60 weight percent 2-ethylhexyl acrylate, (2) 10 to 40 weight percent acrylonitrile, and (3) 20 to 70 weight percent halogenated monomer selected from the class consisti.ng of vinylidene chloride, halogenated phenyl acrylate, halogenated phenyl methacrylate containing 20 to 70 percent by weight of halogen and the fire retardant plasticizer being selected from the class consisting of a triorgano phosphate, alone or in combination with decabromodiphenyl oxide and metal oxides of antimony and zinc.
Preferably, the terpolymer is an addition polymer of 2-ethylhexyl acrylate, acrylonitrile and a third monomer selected from the class consisting of vinylidene chloride, pentachlorophenyl methacrylate and 2,4,6-tribromophenyl methacrylate.
Furthermore and preferably the fire retardant additive contains a triorgano phosphate in combination with at least one complementary additive selected from the class of decabromodiphenyl oxide, antimony o~ide and zinc oxide.
It has been found that the above compositions can be formed into films or other shapes having improved resistance to aging by incorporation of 0.5 to 4 parts, and preferably 1 to 2 parts of a light stabilizer such as
2-(2'-hydroxy-5'-methylphenyl) benzotriazole, called Tinuvin P , per 100 parts of acrylic terpolymer, together with 0.1 to 2.0 parts, and preferably 0.4 to 1 part of an antioxidant. Any of the usual antioxidants for ethylenic * Trade Mark ~
3~33~
double bonds can be utilized, but the preferred ones are 2,o-ditertbutyl-4-methylphenol, called ~Ø 26; ~,5-ditertbutyl-~1-hydroxy-hydrocinnamic acid triester ~ith l,3,5-tris(2-llydroxyethyl)-S-triazine-2,4,6-(II-1, 311, 5H) trione, callecl ~Ø 35; 2-(l-phenylet1lyl)-4-(l-p1lenylet11ylthio) phenol, clso called Ø 45, anc1 2,~,6-tris (3,5-ditortbutyl-4-11yc1roxybenzyl) mositylene, here-ir1clEter cullcc1 ~Ø 2~6.
Technic1ues Eor prèparation of the torpolymors include solut:ion, bulk, emulsiotl and suspension polymerizatlon. Initiators include all the initiators used for free radical polymerizatio1l such as organic peroxides, hydroperoxides, azo or diazo compounds, persulfates, redox systems, etc.
Emulsifiers include anionic, cationic, nonionic, or amphoteric. Modifiers include aliphat:ic, aryl mercaptans and disulfides, - 3a -.~
, f3, ~3~3~
CCl~, CBr~, CllI~ and CHC13, etc. Among these, mercaptans are the pref`erred ones. Crossl:inkers include divinyl ben-zene, tr:iallyl cyanura-te and e-thylene glycol clime-thacrylate, etc.
Polymeriza-tion may be carried o~l-t in -the presence of air, but faster reactions are observed in -the absence of ~` oxygen at -tempera-tures ranging from -30C. to 110C., al though preferred -temperatures range from abou-t 5C, to about 80C.
The acrylic terpolymers useful in this invention can be made by emulsion polymeriza-tion of a mix-ture of monomers A, B and C in desired percentages in a suitable reactor, viz.
an 8-ounce bottle or stirred reactor. Normally all monomers and initiators are charged to reactors, flushed with nitro-gen and then reacted at 50C. to about 32 percent solids in about 24 hours. For instance, a 100 parts of a monomeric mixture of -the desired mixture of monomers A, B and C, -to-ge-ther with 0.25 parts per hundred monomer (phm) potassium persulfate, 0.15 phm of tertiary dodecyl mercaptan, 0.3 phm of divinyl benzene (DVB)9 2.0 phm sodium lauryl sulfate and - 200 phm of distilled water. The reactor was cooled to roomtemperature and the terpolymer recovered by coagulation in 1.5 percent warm aqueous magnesium sulfate solu-tion, water washed and dried at 50C. overnight. Terpolymers consisting of 40/30/30 - 2 EHA/AN/PCMA, 40/30/30 - 2 EHA/AN/TBMA, 20/30/50 - 2 EHA/AN~VDC or 30/30!40 - 2 EHA/AN/VDG were made by the above recipe for use in the following examples where-in all par-ts and percentages are by weight unless otherwise designated. They have good fire retardancy and good tensile :
~4--3313~
strength and elongation and fur-ther exhibit good re-tention of physical proper-ties after 300 hours Accelerometer aging when incorpo.rated witl~ a phosphat;e plasticizer alone or :in combina-tion with comp].emen-tary addi-tives ln 10 -to 20 parts of decabro~odiphen~l oxi.de or tris(beta-chloroethyl) phos-phate, or :in combina-tion wi-th an-timony oxide and zinc oxide.
See Tables 1 and 2 for illus-tra-tion of -this practice.
Those skilled in -the art know that various ingredients such as lubricants, stabilizers~ pigmen-ts, toners, surfac-^tants, ultraviole-t absorbers, an-tioxidants, can be added to the film depending upon the intended use and nature thereof.
Tables 1 and 2 show compositions in accordance with the invention where compounded on a mill on a parts by weight basis using the recipes of Table 1, which was formed in-to a film of -the -thickness shown in Table 2 before determining the physical properties of the films shown in Table 2.
. .
3~3~
~ I I I I I i / \ I I /~ / ~ ,/\
Ll 1 1 1 1 I L~ ~ ~ I
Lr~ L~
V I I ¦ L~ L L
Cq ~ . ~ L L O
I O L L ~ ) C ~
¦ V ~ H
~ ~ ~ .1~ . C; E-l ~
H ~ ~ O I I H
~ I ¦ ~ r-l O O
~ ml ~ i~ C ~
0~ ~i I I 1~ 1 1 1 1 1 1 ~ IE~, r-l l Ll~ I r-i cl~ OL~L~ O LO C
r-l O C\l i I r-l I I I I I I I O
o o ~ ~ H
V ~ o ~
1~3383~
Note: 1. Sample No. lA & lB = 40/30/30-2EHA/AN/PCMA:
No. 2A1 2B & 2C -- 40/30/30-2E~IA/AN/TBMA;
No. 3A, 3B & 3C = 20/30/50-2EHA/AN/VDC;
No. 4A-4~T = 30/30/40-2E~IA/AN/VDC
Note: 2. 0 = Opaque; T = Tra~sparen-t; SE = Self-ex-tinguishing.
rrabl 2 ~_ ~*
Ti~eModulus, Tensile Ultimate Sample expo- psi at S-trength, Elonga-]0 No. ~ 100%~ _ tion~ %
lA O 1280 2290 280 lA 100 1560 1620 140 lA 200 1620 1590 120 lA 300 1640 1640 130 lB o 1090 1710 240 lB 100 1230 1790 290 lB 200 1320 1550 180 lB 300 1310 1870 260 2C 300 1430 2200 240 ~-3B O 1840 2740 ~ 200
double bonds can be utilized, but the preferred ones are 2,o-ditertbutyl-4-methylphenol, called ~Ø 26; ~,5-ditertbutyl-~1-hydroxy-hydrocinnamic acid triester ~ith l,3,5-tris(2-llydroxyethyl)-S-triazine-2,4,6-(II-1, 311, 5H) trione, callecl ~Ø 35; 2-(l-phenylet1lyl)-4-(l-p1lenylet11ylthio) phenol, clso called Ø 45, anc1 2,~,6-tris (3,5-ditortbutyl-4-11yc1roxybenzyl) mositylene, here-ir1clEter cullcc1 ~Ø 2~6.
Technic1ues Eor prèparation of the torpolymors include solut:ion, bulk, emulsiotl and suspension polymerizatlon. Initiators include all the initiators used for free radical polymerizatio1l such as organic peroxides, hydroperoxides, azo or diazo compounds, persulfates, redox systems, etc.
Emulsifiers include anionic, cationic, nonionic, or amphoteric. Modifiers include aliphat:ic, aryl mercaptans and disulfides, - 3a -.~
, f3, ~3~3~
CCl~, CBr~, CllI~ and CHC13, etc. Among these, mercaptans are the pref`erred ones. Crossl:inkers include divinyl ben-zene, tr:iallyl cyanura-te and e-thylene glycol clime-thacrylate, etc.
Polymeriza-tion may be carried o~l-t in -the presence of air, but faster reactions are observed in -the absence of ~` oxygen at -tempera-tures ranging from -30C. to 110C., al though preferred -temperatures range from abou-t 5C, to about 80C.
The acrylic terpolymers useful in this invention can be made by emulsion polymeriza-tion of a mix-ture of monomers A, B and C in desired percentages in a suitable reactor, viz.
an 8-ounce bottle or stirred reactor. Normally all monomers and initiators are charged to reactors, flushed with nitro-gen and then reacted at 50C. to about 32 percent solids in about 24 hours. For instance, a 100 parts of a monomeric mixture of -the desired mixture of monomers A, B and C, -to-ge-ther with 0.25 parts per hundred monomer (phm) potassium persulfate, 0.15 phm of tertiary dodecyl mercaptan, 0.3 phm of divinyl benzene (DVB)9 2.0 phm sodium lauryl sulfate and - 200 phm of distilled water. The reactor was cooled to roomtemperature and the terpolymer recovered by coagulation in 1.5 percent warm aqueous magnesium sulfate solu-tion, water washed and dried at 50C. overnight. Terpolymers consisting of 40/30/30 - 2 EHA/AN/PCMA, 40/30/30 - 2 EHA/AN/TBMA, 20/30/50 - 2 EHA/AN~VDC or 30/30!40 - 2 EHA/AN/VDG were made by the above recipe for use in the following examples where-in all par-ts and percentages are by weight unless otherwise designated. They have good fire retardancy and good tensile :
~4--3313~
strength and elongation and fur-ther exhibit good re-tention of physical proper-ties after 300 hours Accelerometer aging when incorpo.rated witl~ a phosphat;e plasticizer alone or :in combina-tion with comp].emen-tary addi-tives ln 10 -to 20 parts of decabro~odiphen~l oxi.de or tris(beta-chloroethyl) phos-phate, or :in combina-tion wi-th an-timony oxide and zinc oxide.
See Tables 1 and 2 for illus-tra-tion of -this practice.
Those skilled in -the art know that various ingredients such as lubricants, stabilizers~ pigmen-ts, toners, surfac-^tants, ultraviole-t absorbers, an-tioxidants, can be added to the film depending upon the intended use and nature thereof.
Tables 1 and 2 show compositions in accordance with the invention where compounded on a mill on a parts by weight basis using the recipes of Table 1, which was formed in-to a film of -the -thickness shown in Table 2 before determining the physical properties of the films shown in Table 2.
. .
3~3~
~ I I I I I i / \ I I /~ / ~ ,/\
Ll 1 1 1 1 I L~ ~ ~ I
Lr~ L~
V I I ¦ L~ L L
Cq ~ . ~ L L O
I O L L ~ ) C ~
¦ V ~ H
~ ~ ~ .1~ . C; E-l ~
H ~ ~ O I I H
~ I ¦ ~ r-l O O
~ ml ~ i~ C ~
0~ ~i I I 1~ 1 1 1 1 1 1 ~ IE~, r-l l Ll~ I r-i cl~ OL~L~ O LO C
r-l O C\l i I r-l I I I I I I I O
o o ~ ~ H
V ~ o ~
1~3383~
Note: 1. Sample No. lA & lB = 40/30/30-2EHA/AN/PCMA:
No. 2A1 2B & 2C -- 40/30/30-2E~IA/AN/TBMA;
No. 3A, 3B & 3C = 20/30/50-2EHA/AN/VDC;
No. 4A-4~T = 30/30/40-2E~IA/AN/VDC
Note: 2. 0 = Opaque; T = Tra~sparen-t; SE = Self-ex-tinguishing.
rrabl 2 ~_ ~*
Ti~eModulus, Tensile Ultimate Sample expo- psi at S-trength, Elonga-]0 No. ~ 100%~ _ tion~ %
lA O 1280 2290 280 lA 100 1560 1620 140 lA 200 1620 1590 120 lA 300 1640 1640 130 lB o 1090 1710 240 lB 100 1230 1790 290 lB 200 1320 1550 180 lB 300 1310 1870 260 2C 300 1430 2200 240 ~-3B O 1840 2740 ~ 200
4~. 300 1520 2400 220 ~C O 1590 2670 230 4C 100 1980 3060 2~0 ~ ~ 3 ~ ~ ~
Table 2 (continued) Time Modulus, Tensile Ul-timate Sample expo- psi at Strength, Elonga-No.sure~hr 100% psi _ tion, ~F 100 1400 2670 2L~o L~F 200 1420 2850 260 4G 0 l0l~0 2030 200 4G 100 1~70 1580 140 4G 300 1470 2120 200 ..
;~ * Polymer film thickness = 14~26 mils While certain representative embodiments and details - have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein without depart-ing from the spirit or scope of the invention.
.
..~_
Table 2 (continued) Time Modulus, Tensile Ul-timate Sample expo- psi at Strength, Elonga-No.sure~hr 100% psi _ tion, ~F 100 1400 2670 2L~o L~F 200 1420 2850 260 4G 0 l0l~0 2030 200 4G 100 1~70 1580 140 4G 300 1470 2120 200 ..
;~ * Polymer film thickness = 14~26 mils While certain representative embodiments and details - have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein without depart-ing from the spirit or scope of the invention.
.
..~_
Claims (3)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A flame retardant polymer film comprising a terpolymer and about 10 to 40 parts of a fire retardant plasticizer per 100 parts of polymer, said torpolymer being a reaction product of (1) 20 to 60 weight percent 2-ethylhexyl acrylate, (2) 10 to 40 weight percent acrylonitrile, and (3) 20 to 70 weight percent halogenated monomer selected from the class consisting of vinylidene chloride, halogenated phenyl acrylate, halogenated phenyl metha-crylate containing 20 to 70 percent by weight of halogen and the fire retardant plasticizer being selected from the class consisting of a triorgano phosphate, alone or in combination with decabromodiphenyl oxide and metal oxides of antimony and zinc.
2. The film of claim 1 wherein the terpolymer is an addition polymer of 2-ethylhexyl acrylate, acrylonitrile and a third monomer selected from the class consisting of vinylidene chloride, pentachlorophenyl methacrylate and 2,4,6-tribromophenyl methacrylate.
3. The film of claim 1 wherein the fire retardant additive contains a triorgano phosphate in combination with at least one complementary additive selected from the class of decabromodiphenyl oxide, antimony oxide and zinc oxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US751,935 | 1976-12-17 | ||
| US05/751,935 US4110296A (en) | 1976-12-17 | 1976-12-17 | Fire retardant acrylic terpolymer composition and films thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1103830A true CA1103830A (en) | 1981-06-23 |
Family
ID=25024153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA290,361A Expired CA1103830A (en) | 1976-12-17 | 1977-11-07 | Fire retardant acrylic terpolymer composition and films thereof |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4110296A (en) |
| CA (1) | CA1103830A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4524170A (en) * | 1983-04-25 | 1985-06-18 | Milliken Research Corporation | Flame retardant finishing composition for synthetic textiles |
| DE3636401A1 (en) * | 1986-10-25 | 1988-04-28 | Hoechst Ag | TRANSPARENT POLYMER MATERIAL |
| DE3636399A1 (en) * | 1986-10-25 | 1988-05-05 | Hoechst Ag | OPTICAL FIBER |
| US4927873A (en) * | 1988-03-25 | 1990-05-22 | Pennwalt Corporation | Halophenyl ester flame retardants for polyphenylene ether resins |
| US5043374A (en) * | 1988-03-25 | 1991-08-27 | Atochem North America, Inc. | Halogenated polyester flame retardants for polyphenylene ether, polyolefin and polyethylene terephthalate resins |
| IL86605A (en) * | 1988-06-02 | 1992-02-16 | Bromine Compounds Ltd | Process for the polymerization of pentabromobenzylester monoacrylate |
| EP0421610B1 (en) * | 1989-09-28 | 2003-05-14 | Bromine Compounds Ltd. | Flame retardant compositions |
| US5883144A (en) * | 1994-09-19 | 1999-03-16 | Sentinel Products Corp. | Silane-grafted materials for solid and foam applications |
| AU6326796A (en) * | 1996-03-05 | 1997-09-22 | Conrad L. Hinsley Jr. | Fire-retardant adhesive thermoplastic film |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2949432A (en) * | 1957-09-12 | 1960-08-16 | Chemstrand Corp | Fiber-forming composition containing an acrylonitrile polymer plasticized with tri-(2-ethylhexyl) phosphate |
| US3061571A (en) * | 1960-03-21 | 1962-10-30 | American Cyanamid Co | Flame retardant composition comprising an acrylonitrile cross-linked polyester resinand an organic phosphate |
| BE624340A (en) * | 1961-11-02 | |||
| NL125094C (en) * | 1962-07-23 | 1963-07-28 | ||
| US3300423A (en) * | 1963-12-12 | 1967-01-24 | Nat Starch Chem Corp | Antimony oxide-vinylidene chloride copolymer emulsions |
| US3715310A (en) * | 1968-07-17 | 1973-02-06 | Bakelite Xylonite Ltd | Fire-retardant compositions |
| DE2202791A1 (en) * | 1972-01-21 | 1973-08-02 | Roehm Gmbh | FLAMEWORK ACRYLIC GLASS |
| US3929688A (en) * | 1972-04-07 | 1975-12-30 | Stauffer Chemical Co | Bis(2,3-dibromopropyl)phosphate as a flame retardant for polymers |
| JPS5516181B2 (en) * | 1972-04-21 | 1980-04-30 | ||
| US3912792A (en) * | 1972-08-04 | 1975-10-14 | M & T Chemicals Inc | Flame retardant compositions |
-
1976
- 1976-12-17 US US05/751,935 patent/US4110296A/en not_active Expired - Lifetime
-
1977
- 1977-11-07 CA CA290,361A patent/CA1103830A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US4110296A (en) | 1978-08-29 |
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